Process for breaking petroleum emulsions



Patented June 24, 1930 NITED ST FATE OFF-ICE MELVIN DE GROOTE, OE ST.LOUIS, AN D BERNHARD KEISER, OF WEBSTER GROVES, MIS- SOURI, ASSIGNORS TOWM. S. BARNICKEL & COMPANY, OF WEBSTER GROVES, MIS- SOURI, A CORPORATIONOF MISSOURI PROCESS FOR BREAKING PETROLEUM EMULSIONS No Drawing.

monly referred to as cut oil, roi'ly oil,

emulsified oil, and bottom settlings.

The object of our invention is to provide a novel and inexpensiveprocess for separating emulsions of the character referred to into theircomponent parts of oil and water or brine.

Briefly described, our process consists in subjecting a petroleumemulsion of the water-in-oil type to the action of a treating agent ordemulsifyingagent of the kind hereinafter described, thereby causing the5 emulsion to break down and separate into its component parts of oiland water or brine, when the emulsion is permitted to re- I main in aquiescent state after treatment.

The treating a ent employed in our process consists o a substitutedsulfonic aromatic body derived by the action of a condensing agent andsulfonating agent on an aromatic odfy, an aldehyde and an organicdetergentorming body. In producing said treating agent an aldehyderesidue derived from an aliphatic aldehyde, such as formaldehyde oraraldehyde, of a cyclic aldehyde such as rfural, or an aromatic aldehydesuch as bdnzaldehyde, is intro duced' into an aromatic nucleus,particularly a polycyclic aromatic nucleus. The aromatic material mayconsist of benzene, toluene, naphthalene, anthracene, naphthacene, orother substances having similar properties. Instead of using theunaltered aromatic body, derivatives may be employed, such as halogenderivatives, nitro derivatives, hydrogenated derivatives, or hydroxyderivatives. If desired, the sulfonic group 50 may be introduced intothe aromatic body Application filed January 21, 1929. serial No,334,110.

before the introduction of the aldehyde residue of the kind described;for instance, benzene or naphthalene sulfonic acid, or beta naphtholsulfonic acid may be employed. The general method of manufacturingtreating agents of' the kind employed by our process is simply one ofmixing the aromatic body, aldehyde and organic detergent-forming body,and subjecting the mixture to the action of a sulfonating agent and acondensing agent with extremely cautious control. When such material assulfuric acid, oleum, chloro-sulfonic acid, or othersubstances havingsimilar proper ties. is cautiously employed, said. material acts both asa sulfonating agentand a condensing agent at the same time. If anaromatic sulfonic body is employed, together with an aldehyde, it isonly necesary to employ a condensing agent. It may be possible tointroduce more than one aldehyde residue into'an aromatic body; forinstance, two or more moles of formaldehyde can be introduced into onemole of naphthalene. Furthermore, after the introduction of one or morealdehyde residuesinto the aromatic body, it is still possible tointroduce other residues into the aromatic body, such as alcoholresidues derived from aliphatic, aralkyl, aromatic, or cyclic'alcohols.

The organic detergent-forming body may be a fatty residue or an organicdetergentforming group ofthe type subsequently described. It isintroduced into the aromatic nucleus in addition to the aldehyde residueby a reaction akin to the formation of a Twitchell. reagent for use inthe art of fat splitting. Thus, it is to be understood that one or morealdehyde residues of the same kind or different kinds can be introducedinto the aromatic body, and that in addition to said aldehyde residue,there is introduced kind previously mentioned, such as a fatty residue.

Just as it would be possible to mix one .mole of formaldehyde with onemole ofmatic nucleus, so itwould be possible to an organicdetergent-forming residue of the mix one mole of formaldehyde with onemole of a fatty material and mix same with an aromatic body plussuflicient sulfuric acid to produce solution, and thereby introduce analdehyde residue and a fatty residue into the aromatic body. It mighteven be possible to introduce both an alcohol residue and a fattyresidue into the aromatic bodyin addition to the aldehyde residue.

The fatty residue referred to in the procedure above described can bereplaced by any organic detergent-forming residue. An

. taining about 37%, by weight, is mixed with one mole of finelypowdered naphthalene, and agitated, with the addition of one mole ofcastor oil. When these three materials are thoroughly mixed, and whilethey are continuously agitated, a suitable sulfonating agent, such assulfuric acid, is added very cautiously, with only a moderate rise intem- Eerature. Said temperature rise is controlled y means of coolingcoils. When sufficient acid is added to give a completely soluble mass,said reaction is continued with the addition of oleum or chloro-sulfonicacid, if required, to give a reaction mass, which, on cautious dilutionwith water, gives an upper layer which is water-soluble, after beingfreed from the excess acid. When sulfonation 'is complete, as determinedby the above test, themass is carefully diluted with water until anupper layer separates. The upper layer is'drawn off and neutralized withany suitable base such as caustic soda, caustic potash, or ammonia. Weprefer to use ammonia.

Although the composition of condensation products of the kind hereindescribed is largely a matter of conjecture, due to the scarcity ofsuitable analytical data, yet the roduct can be readily prepared byfollowlng the described manufacturing process,

and its composition can be approximated from well known kindredreactions, such as is disclosed in the following patents, to wit:

U. S. Patent N 0. 628,503, to Twitchell, which describes adi-substituted aromatic body (a Twitchell reagent) in which one hydrogenof'th'e aromatic is replaced by the sulfonic acid group $0 11, andanother is replaced by the fatty acid residue. Indicating an aromaticresidue by R and the fatty radical such as an ethyl radical.

acid residue by F, this product may be written as FRSO H.

U. S. Patent No. 1,670,505, to Gunther, de-

scribes a similar compound, except that the- It is recognized, asindicated in U. S. Pat

ent No; 1,722,904, to Somerville, that the alcohol residue A in priorexamples may be replaced by the aldehyde residue L.

Thus, the compound AFRSOJ-I has a counterpart, LFRSO H, which isprobably the chief constituent of the present applica tion. In thiscompound the aromatic body has three substituting groups therefor, onealdehyde residue, one fatty residue, and one sulfonic residue. I

However, as shown by German Patent No. 226,222, to Meister Lucino andBruning,

the aldehyde residue L may be attached to the fatty residue F in whichcase there would be produced an isomeride of the same empirical formulaLFRSO H. This would differ from the previously described isomer in thatthe aldehyde residue, instead of being attached to the aromatic nucleusR, is attached to the fatty residue F. The fatty residue F and thesulfonic group SOgI-I are gagttached-to the aromatic nucleus R, asbeore. 1

The material or substance above described can be employed as an acidmass to treat a petroleum emulsion, but this is not desirable, due toits corrosive effect. There is no objection to an excess of alkali, ifdesired. Such material can also be converted into an ester byesterification in. the usual manner to produce an aromatic or aliphaticester such as the ethyl ester. Some of the esters so produced may beoil-soluble, such as the hexyl ester. p

The'treating agent, when it is ready for use, may be acidic in nature,and the complex substituted aromatic sulfonic group may be united withan acid hydrogen ion, as is the case when the acid itself is employed.When said acidic material is neutralized, the hydrogen ion is replacedby, a suitable metallic ion equivalent such as a true metallic ion or anammonium radical. In the event that the material is esterified, thehydrogen ion is replaced by an'organic We will refer to the hydrogen ionor its metallic substitute or its organic substitute as the hydrogen ionequivalent.

The form, state or condition of the treating agent at the time it ismixed with or treated, may be varied to suit existing conditions. It canbe used in substantially anhydrous state or in solutions of anyconvenient strength. A concentrated solution can be emulsified into oilby agency of any suitable oil-soluble emulsifier such as calcium oleate.

The treating agent can be formed entirely or demulsifying agent of thekind above described may be brought in contact with the v emulsion tobe" treated in any of the numerous ways now employed in the treatment ofpetroleum emulsions of the water-in-oil type with. chemical demulsifyingagents, such,

for example, as by introducing the treating agent into the well in whichthe emulsion is produced; introducing the treating agent into a conduitthrough which theemulsion is flowing; introducing the treating agentinto a tank in which the emulsion is stored, or introducing the treatingagent into a container that holds a sludge obtained from the bottom ofan old storage tank. In some instances it may be advisable to introducethe treating agent into a producing well in such a way that it willbecome mixed with water and oil that are emerging from the surroundingstrata, before said water and oil enter thebarrel of the well pump orthe tubing up through'which said water and oil flow to the surface ofthe ground. After treatment the emulsion is allowed to stand in aquiescent state, usually in a settling tank, at a temperature varyingfrom atmospheric temperature to about 200 F., so as to permit the wateror brine to separate from the oil, it being preferable to keep thetemperature low enough so. as to prevent the valuable constituents ofthe oil from volatilizing. If desired, the treated emulsion may be actedupon by one or the other of various kinds of ap aratus now used in theoperation of brea ng petroleum emulsions, such as homogenizers, haytanks, gun barrels, filters, centrifuges or electrical dehydrators.

The amount of treating agent on the an- .hydrous basis that is requiredto break the emulsion may vary from approximately l part of treatingagent to 500 parts of emulsion, up to a ratio of 1 part of treatingagent to 20,000 parts of emulsion, depending upon the type or kind ofemulsion being 1 emulsions, i. e., emulsions that will yield readily tothe action of chemical demulsifying agents, the maximum ratio abovementioned will frequentlyproduce highly satisfactory results. For theaverage petroleum emulsion of the water-in-oil type a ratio of 1 part oftreating agent to 5,000 parts of emulsion will usually be found toproduce commercially satisfactory results.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent of the United States is:

1. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of ademulsifying agent comprising a sulfonic body derived from thecondensation of an aromatic body, an aldehyde, and an organicdetergent-forming body.

2. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising a sulfonic body derived fromthe condensation of an aromatic body, an alde- {)lyle, and an organicdetergent-forming 3. A process for. breaking a petroleum emulsion of thewater-in-oil type, which consists in subjecting the emulsion to theaction of a water-soluble demulsifying'agent comprising a water-solublesalt of a sulfonic body derived from the condensation of an aromaticbody, an aldehyde, and an organic detergent-forming body.

4. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising an ammonium salt of asulfonic body derived from the condensation of an aromatic body, analdehyde, and an organic detergent-formin body.

5.. A process or breaking a petroleum emulsion of the water-in-oil'type, which consists in subjecting the emulsion to theaction of a.demulsifying agent comprising a sulfonic body derived from thecondensation of a bicyclic aromatic body, an aldehyde, and an organicdetergent-formim body.

6. A process for breaking a petroleum emulsion of the water-in-oil typewhich consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising a sulfonic body derived fromthe condensation of a bicyclic aromatic body, an aldehyde, and anorganic detergent-forming body.

7. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising a water-soluble salt of asulfonic body derived from the condensation of abicyclic aromatic body,an aldehyde, and an organic detergent-forming body.

8. A process for breaking a petroleum emulsion of the water-in-oil type,which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising an ammonium salt of asulfonic body derived from' the condensation of a bicyclic aromaticbody, an aldehyde, and

an organic detergent-forming body.

9. A*process for breaking a petroleum emulsion of the water-in oil'type,which consists in subjecting the emulsion to the action of ademulsifying agent comprising a sulfonic body derived from thecondensation of a bicyclic aromatic body, an aldehyde, and a fatty body.

10. A process for breaking a petroleum emulsion of the Water-in-oiltype, which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising a sulfonic body derived fromthe condensation of a bicyclic aromatic body, an aldehyde, and a fattybody.

11. A process forbreaking a petroleum emulsion of the Water-in-oil type,which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising a water-soluble salt of asulfonic body derived from the condensation of a bicyclic aromatic body,an aldehyde, and a fatty body.

12. A process for breaking a petroleum emulsion of the Water-in-oiltype, which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising an ammonium salt of asulfonic body derived from the condensation of a bicyclic aromatic body,an aldehyde, and a fatty body.

13. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to. the action of a'demulsifying agent comprising a sulfonic body derived from thecondensation of a bicyclic aromatic body, an aliphatic aldehyde, and afatty body.

. 14. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion. to the action of awater-soluble demulsifying agent comprising a sulfonic body derived fromthe condensation of a bicyclic aromatic body, an

aliphatic aldehyde, and a fatty body. 1

15. .A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of a water-soluble demulsifying, agent comprising a water-soluble salt of asulfonic body derived from the condensation of a bicyclic aromatic bodyan aliphatic aldehyde, and a fatty, body.

16. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising an ammonium salt of asulfonic body derived from the condensation of a bicyclic aromatic body,analiphatic aldehyde, and a fatty body. I

' 17. A process for breaking a petroleum emulsion of the water-in-oiltype, which'consists in subjecting'the emulsion to the action of ademulsifying agent comprising a sulfonic body derived from thecondensation of a bio clic aromaticbody, formaldehyde, and a fatty body.

18. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of awater-soluble demulsifying agent comprising a sulfonic body derived fromthe condensation of a bicyclic aromatic body, formaldehyde, and a fattybody.

19. A process for breaking a petroleum emulsion of the water-in-oiltype, which consists in subjecting the emulsion to the action of aWater-soluble demulsifying agent comprising water-soluble salt of asulfonic body derived from the condensation of a bicyclic aromatic body,formaldehyde, and a fatty body.

20. Aprocess for breaking a petroleum emulsion of the Water-in-oil-type,which consists in subjecting the emulsion to the 'action of awater-soluble demulsifying agent comprising an ammonium salt of asulfonic body derived from the condensation of a bicyclic aromatic body,formaldehyde, and

